Studies on monobactams II. Synthesis and β-lactamase inhibitory activity of 4α-methyl-3-[(thien-2-yl)-methylene]-2-azetidinone-1-sulfonate

Two monobactam derivatives, potassium 4-methyl-(3E)-[(thien-2-yl)methylene]-2-azetidinone-1-sulfonate and its (3Z)-isomer, were prepared and evaluated for their -lactamase inhibitory activities. These compounds were devoid of -lactamase inhibitory activity.SynPhar Laboratories Inc., #2, 4290-91A Street, Edmonton, Alberta T6E 5V2, Canada. Tokushima Research Institute, Taiho Pharmaceutical Co., Ltd., 224-2 Ebisuno Hiraishi, Kawauchi-cho, Tokushima 771-01, Japan. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1548–1552, November, 1998.     

Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation

Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR₃)_n to give benzoylnickel complexes, PhCONi(acac)PR₃ (R = Ph, Et, cyclo-C₆H₁₁), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh₃ in acetone was studied by NMR, and found to be first order in the benzoylnickel complex.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Simultaneous ultramicrodetermination of heterogeneous halogens in organic compounds

The simultaneous ultramicrodetermination of heterogeneous halogens in organic compounds was carried out by the potentiometric titration with 0.002 M silver nitrate after the sample was decomposed by the flask combustion method. In examination of the titration, it was found that clear potential break at the end point was obtained by controlling the delivery speed of the titrant at 0.2 ml/min or slower and the temperature of the solution to be titrated at ca. 10 °C when chloride ion is present. The error due to coprecipitation during the titration and the effect of the mole ratio of heterogeneous halide ions in the sample solution was examined and discussed. The analysis of organic halogen compounds resulted in an error of within 0.4% and standard deviation of less than 0.25%.     

Aminyl radical cyclization by means of anodic oxidation. Stereoselective synthesis of cis-1-methyl-2,5-disubstituted pyrrolidines

Neutral aminyl radicals generated by anodic oxidation of lithium alkenylamides 2 undergo a stereoselective cyclization to give $\text{cis}$-1-methyl-2,5-disubstituted pyrrolidines 4. Their $\text{cis}$ stereochemistry was confirmed by a comparison with $\text{trans}$-1,2-dimethyl-5-phenylpyrrolidine, the structure of which was established by X-ray crystallographic analysis of its quarternary ammonium bromide 6.     

Supramolecular hydrogels and organogels based on novel l-valine and l-isoleucine amphiphiles

New low-molecular-weight gelators based on l-valine and l-isoleucine gelators, which have a positively charged terminal group, can gel not only pure water and aqueous solutions containing inorganic acids and salts but also some organic solvents and oils.     

Pictet-Spengler reactions catalyzed by Brønsted acid-surfactant-combined catalyst in water or aqueous media

Perfluorooctanesulfonic acid (PFOSA), Brønsted acid-surfactant-combined catalyst, efficiently catalyzes the Pictet-Spengler reactions of β-arylethyl carbamate derivatives with aldehydes in water. The present reaction is accelerated by the addition of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP).